CN102131839A

CN102131839A - Adhesive composition adapted for bonding large mass parts to structures

Info

Publication number: CN102131839A
Application number: CN200980132627XA
Authority: CN
Inventors: 迪特马尔·戈隆波斯基
Original assignee: Dow Global Technologies LLC
Current assignee: Dow Global Technologies LLC
Priority date: 2008-08-22
Filing date: 2009-07-14
Publication date: 2011-07-20
Anticipated expiration: 2029-07-14
Also published as: CN102131839B; JP2012500862A; KR101650965B1; KR20110068978A; EP2318448A1; WO2010021793A1; EP2318448B1; BRPI0912919B1; US8668804B2; JP5669735B2; BRPI0912919A2; US20110108183A1

Abstract

The invention relates to a two-part composition comprising: A) in one part (i) one or more isocyanate functional prepolymers; and B) in a second part(ii) one or more compounds having isocyanate reactive groups; (iii) one or more fillers selected such that the composition is nonconductive; (iv) one or more catalysts for the reaction of isocyanate groups with active hydrogen containing compounds wherein either or both of the one or more isocyanate functional prepolymers and the one or more compounds having isocyanate reactive groups have solid organic particles grafted thereto such that the composition contains from about 6 to about 13 percent by weight of the total composition of solid organic particles. In a preferred embodiment, the second part comprises from about 35 to about 65 percent by weight of one or more compound having isocyanate reactive groups which have solid organic particles grafted to the backbone. In another preferred embodiment, the one or more isocyanate functional prepolymers comprise about 14 to about 20 percent by weight of solid organic particles grafted to the backbone of the prepolymers. In another preferred embodiment, the solid particles comprise a thermoplastic polymer or rubber-modified thermoplastic polymer.

Description

Be suitable for big quality part is bonded to binder composition on the structure

The requirement of applying date rights and interests

The application requires the applying date rights and interests of the U.S. Provisional Application series 61/090,986 of submission on August 22nd, 2008, is in various purposes this U.S. Provisional Application series 61/090,986 is attached to this by reference.

Invention field

The present invention relates to comprise two portions composition of isocyanate-functional component and isocyanate-reactive component.The present invention relates to the method for using this two portions composition that substrate is bonded together, and relate to and comprise the structure that uses the substrate of said composition agglutinating.In the preferred construction body, buildings and carrier vehicle are arranged.

Background of invention

Composition with isocyanate-functional component is used to substrate is bonded together.A kind of common use of such composition is to bond glass in the structure, and described glass is the form of window normally.In automobile composing room, window usually uses a part (one part) binder composition that contains the isocyanate-functional component and in being bonded in.Typically, these compositions are by solidifying with the reaction of environment moisture.Use a part of tackiness agent, because distribution and applying adhesive devices needed are not as being used to apply the equipment complexity of two-part adhesive composition.Part moisture solidification tackiness agent typically expends several hours and is cured.In composing room's environment, the vehicle several hrs does not drive, and this slow curing is acceptable.A part of moisture solidification tackiness agent as known in the art is disclosed in: United States Patent (USP) 4,374,237, United States Patent (USP) 4,687,533, United States Patent (USP) 4,780, and 520, United States Patent (USP) 5,063,269, United States Patent (USP) 5,623, and 044, United States Patent (USP) 5,603,798, United States Patent (USP) 5,852, and 137, United States Patent (USP) 5,922,809, United States Patent (USP) 5,976, and 305, United States Patent (USP) 5,852,137 and United States Patent (USP) 6,512,033, relevant portion is combined in this by reference.The example of a part of tackiness agent that is purchased comprises can be available from the BETASEAL of Dow Chemical (Dow Chemical Company) ^TM15630,15625,61355 tackiness agents can be available from the EFBOND of Eftec ^TMThe windshield glass tackiness agent can be available from the WS 151 of Yokohama Rubber Company ^TM, WS212 ^TMTackiness agent, and can be available from the SIKAFLEX of Sika Corporation ^TMTackiness agent.

In a part, contain isocyanate functional compound or prepolymer and in another part, contain compound and/or two portions composition of prepolymer uses in curing speed has the situation of importance with isocyanate-reactive component.A kind of such environment is to replace in the glass industry after sale at automobile.Usually, client wishes the tackiness agent fast setting, so that vehicle can drive after the displacement window is bonded in the vehicle as soon as possible.The advantage of two-part adhesive is that curing reaction carries out with the speed of reaction more faster than a part of moisture solidification adhesive composition.Contain isocyanate functional compound or prepolymer and contain compound with isocyanate-reactive component and/or the example of two portions composition of prepolymer is disclosed in another part in a part: EP 1,524,282, United States Patent (USP) 5,852,103, United States Patent (USP) 6,709,539, United States Patent (USP) 7,101,950 and United States Patent (USP) 7, in 361,292, relevant portion is combined in this by reference.

Use tackiness agent in such as railway carriage and head, motorbus and truck big window being bonded to big carrier vehicle.The quality of these windows produces needs for the tackiness agent with one group of unique performance.Especially need have the tackiness agent of good green strength after coating in the short period of time, typical a part of tackiness agent can not provide such green strength character.In addition, the open hour that adhesive composition need be longer than the open hour that typical two-part adhesive allowed, promptly be coated to the substrate beginning and no longer can be adhered to the suprabasil time up to tackiness agent from tackiness agent.15 minutes to 30 minutes open hour are ideal.Therefore, what need is a kind of two-part adhesive system that shows good green strength, this two-part adhesive system had by coating the ability of big quality window fix in position and longer open hour, thus allow slower sealing agent coating and packaging technology and allow window with can regulate window after window frame contacts.

Summary of the invention

The present invention is a kind of two portions composition, and described composition comprises: A) one or more isocyanate-functional prepolymers of (i) in a part; And B) in second section (ii) one or more have the compound of isocyanate-reactive group; (iii) selected one or more fillers are so that described composition is non-conductive; (iv) one or more catalyzer, described catalyzer is used for isocyanate groups and contains the reaction of compound bearing active hydrogen: wherein said one or more isocyanate-functional prepolymers and described one or more have compound arbitrary of isocyanate-reactive group or both have the SOLID ORGANIC particle that is grafted on it, make described composition contain to account for about 6 SOLID ORGANIC particles to about 13 weight % of total composition.In a preferred embodiment, second section comprise about 35 to about 65 weight % one or more have the compound of isocyanate-reactive group, described compound with isocyanate-reactive group has the SOLID ORGANIC particle that is grafted on the skeleton.In another preferred embodiment, described one or more isocyanate-functional prepolymers comprise about 14 SOLID ORGANIC particles to the skeleton that is grafted to prepolymer of about 20 weight %.In another preferred embodiment, described solids comprise the thermoplastic polymer of thermoplastic polymer or modified rubber.

In another embodiment, described invention is a kind of method that plural substrate is bonded together, described method comprises: make according to two portions composition contact of the present invention, and the contacted part of described composition contacted with plural substrate, wherein the contacted part at described composition is set between the substrate, thereby described substrate is bonded together.In a preferred embodiment, a substrate is a glass, window preferably, and another substrate comprises the structure of glassy bond on it, preferably buildings or carrier vehicle.

Composition of the present invention can be used as the tackiness agent that substrate is bonded together.Various substrates can be used described composition bond together, and described substrate for example is substrate of plastics, glass, timber, pottery, metal, coating or the like.Composition of the present invention can be used for the not similar substrate of class Sihe is bonded together.Described composition is used in particular for bonding glass to other substrate such as on vehicle and the buildings.Composition of the present invention also can be used for the built-up type assembly such as the parts bonding of vehicle combination formula assembly together.Can bond glass to vehicle on coating and uncoated part.Composition of the present invention provides enough green strengths, thereby the goods that allow big quality are such as window short period of time fix in position after this big quality goods are bonded in the other substrate.In addition, composition of the present invention provides the sufficiently long open hour, thereby allows big quality goods to contact and goods adjusting relative to each other with the suitable of another substrate.

Detailed Description Of The Invention

In order to realize the required character of composition of the present invention, in first part is isocyanate-functional prepolymer in the A part, or be the compound with isocyanate-reactive group in the B part at second section, perhaps they both have a SOLID ORGANIC particle on the skeleton that is grafted to them.Can be grafted in first part is the isocyanate-functional prepolymer in the A part or on second section was the compound with isocyanate-reactive group in the B part, perhaps the SOLID ORGANIC particle on they both comprised: any particle that improves composition elastic property of the present invention and green strength when two portions are combined.Preferred SOLID ORGANIC particle comprises the thermoplastic polymer particle of thermoplastic polymer or modified rubber.Preferred thermoplastic is based on the thermoplastic polymer of monovinylidene aromatic monomer and the multipolymer of monovinylidene aromatic monomer and conjugated diolefine, acrylate, methacrylic ester, unsaturated nitrile or their mixture.Multipolymer can be block or random copolymers.More preferably, organic filler comprises one or more multipolymers of unsaturated nitrile, conjugated diolefine and monovinylidene aromatic monomer and/or one or more multipolymers of unsaturated nitrile and monovinylidene aromatic monomer.Also more preferably, described particle comprises styrene-acrylonitrile copolymer.Organic polymer particle preferably has for elastic property and the enough big granularity of green strength of improving final solidified tackiness agent, but this granularity can be greatly to reducing the final strength of tackiness agent after solidifying.Preferably, granularity is about more than 10 microns, and more preferably granularity is about more than 20 microns.Preferably, granularity is about below 50 microns, and more preferably granularity is about below 40 microns.Composition comprises the organic polymer particle of q.s, make: tackiness agent has enough green strengths when contact component, thereby before completely solidified with big quality goods fix in position, thereby showing the sufficiently long open hour allows big quality goods to want contacting of agglutinating structure with big quality goods, regulates the position of big quality goods; And the amount of organic polymer particle is not too large to make: cure adhesive has too many elasticity, and described elasticity is limited by elongation.Preferably, composition according to the present invention has sufficient intensity for required purposes by curing.Preferably, based on the gross weight of described composition, described composition contains the above organic polymer particle of 6 weight % of having an appointment, more preferably from about more than the 7 weight %, and most preferably from about more than the 8 weight %.Preferably, based on the gross weight of described composition, described composition contains the following organic polymer particle of 13 weight % of having an appointment, more preferably from about below the 12 weight %, and most preferably from about below the 10 weight %.

Organic filler is arranged in the embodiment of the part with isocyanate-functional prepolymer therein, and such part preferably comprises the organic filler of the amount that realizes character noted earlier.Preferably, be the weight of part A based on first part, the isocyanate-functional prepolymer has the organic polymer particle greater than 0 weight % that is grafted on it, more than preferred about 4 weight % and most preferably from about more than the 6 weight %.Preferably, be the weight of part A based on first part, the isocyanate-functional prepolymer has the following organic polymer particle of about 26 weight % that is grafted on it, below preferred about 20 weight %, and more preferably from about below the 14 weight %.Organic filler is arranged in the embodiment of the part with isocyanate-reactive compound therein, and such part preferably comprises the organic filler of the amount that realizes character noted earlier.Preferably, be the weight of part B based on second section, isocyanate-reactive compound has the above organic polymer particle of about 12 weight % that is grafted on it, and most preferably from about more than the 14 weight %.Preferably, be the weight of part B based on second section, the compound that contains isocyanate-reactive group has the following organic polymer particle of about 26 weight % that is grafted on it, most preferably from about below the 20 weight %.

Composition of the present invention comprises two portions, and first part is a part A, and it comprises one or more isocyanate-functional prepolymers, and second section is part B, and it comprises one or more compounds that contains one or more isocyanate-reactive compounds.Isocyanate-reactive compound and the reaction of isocyanate-functional prepolymer form cured compositions, and this cured compositions shows good bond property to a lot of substrates.By making two portions contact, described composition and isocyanate-reactive group begin to react with isocyanate groups.The final curing of the composition of combination expends some times and realizes finishing.The required open hour are provided to composition like this." open hour " are understood to mean after two portions contacts up to mixture and begin to become the high viscosity paste and do not meet with distortion with the shape that meets second substrate and be not adhered to time on it in assembling process.Preferably, the open hour are about more than 8 minutes, and more preferably about more than 15 minutes.Preferably, the open hour are below 30 minutes, and are more preferably about below 25 minutes, and most preferably are about below 20 minutes.The compositions table of combination reveals foregoing required green strength.Preferably, tackiness agent shows the lap shear strength more than the 0.6MPa after 60 minutes, and more preferably about 0.8Mpa is above and most preferably be more than about 1.0MPa, and described lap shear strength is definite according to DIN 53283.Composition is in case combination just shows consistent character in wide temperature limit.Preferably, to about 45 ℃ temperature range, has very little variation at about 0 ℃.

" one or more " used herein are meant at least a, or can use as open more than a kind of mentioned component." nominal (Nominal) " that use about functionality is meant theoretical functionality, and this can use the stoichiometry of component to calculate to some extent usually.Normally, actual functionality is different, owing to undesirable, the incomplete conversion of reactant that is raw material and the formation of by product.

First part comprises one or more isocyanate-functional prepolymers.Described one or more isocyanate-functional prepolymers can pass through prepared by any suitable process, such as by make have more than the compound of one isocyanate-reactive group such as polyamines and polyvalent alcohol (glycol, three pure and mild dispersion triols are such as copolymer polyols or grafted triol) with surpass stoichiometric one or more excessive polymeric polyisocyanates, have isocyanate functionality and satisfy reaction under the reaction conditions of prepolymer of free isocyanate content that this paper discusses standard and prepare being enough to form.At a kind of preferred method that is used for preparing prepolymer, polymeric polyisocyanate and one or more glycol, one or more three pure and mild one or more dispersion triols and one or more optional amine terminated polyether reactions.Have more than the compound of one isocyanate-reactive group and exist with the amount of most isocyanate groups reactions being enough to, thereby stay enough isocyanate groups, to meet the free isocyanate content in the required prepolymer.The isocyanate-functional prepolymer can be by any suitable method such as mass polymerization and solution polymerization.The preferred ingredient that is used to prepare the isocyanate-functional prepolymer is disclosed in people's such as Zhou 7,361,292, and relevant portion is combined in this by reference.The preferred method that is used to prepare prepolymer is disclosed in United States Patent (USP) 5,922,809 the 9th hurdle, and 4 to 51 row, it is combined in this by reference.

The preferred polymeric polyisocyanate that is used to prepare prepolymer is included in United States Patent (USP) 5,922, and 809 the 3rd hurdles 32 walk to those disclosed in the 4th hurdle 24 row, and this United States Patent (USP) is combined in this by reference.Preferably, polymeric polyisocyanate is aromatics or alicyclic polymeric isocyanate, such as ditan-4, and 4 '-vulcabond, isophorone diisocyanate, tetramethylxylene diisocyanate, and most preferably be ditan-4,4 '-vulcabond.Two pure and mild triols are generically and collectively referred to as polyvalent alcohol.Can be used for polyvalent alcohol among the present invention and be corresponding at United States Patent (USP) 5,922,809 the 4th hurdle the 60th walks to two pure and mild triols of the polyvalent alcohol of describing in the 5th hurdle the 50th row, and this United States Patent (USP) is combined in this by reference.Preferably, polyvalent alcohol is a polyether polyol, more preferably polyoxyalkylenes ether (polyoxyalkylene oxide) polyvalent alcohol.Most preferred triol is oxyethane-end capped polyvalent alcohol, and this oxyethane-end capped polyvalent alcohol has one or more compound bearing active hydrogen such as glycerine and propylene oxide reaction by making, and then product and reacting ethylene oxide is prepared.

In an aforesaid embodiment, prepolymer comprises one or more and is grafted to organic polymer on the skeleton.Preferably, the particle of organic polymer by organic polymer is included in the prepolymer comprising of dispersion triols of being dispersed in wherein.The 4th hurdle 13 that preferred dispersion triols is disclosed in the United States Patent (USP) 6,709,539 of Zhou walks in the 6th hurdle 18 row, and this United States Patent (USP) is combined in this by reference.Preferred polyhydric alcohols being used for preparing the isocyanate-reactive prepolymer comprises SPECFLEX ^TMNC 700 copolymer polyols; VORALUX available from Dow Chemical ^TMHL 430 copolymer polyols, and available from the ARCOL of Bayer ^TM1096 copolymer polyols.

Preferably, the polyoxyalkylenes ether triol comprises and has the end capped polyoxytrimethylene chain of polyoxyethylene.Preferably, the molecular weight of employed triol is about more than 4,000, and is more preferably about more than 5,000 and most preferably be about more than 6,000.Preferably, the molecular weight of such triol is about below 8,000 and more preferably about below 7,000.Particle can be dispersed in the triol or be grafted on some the skeleton in the triol.Preferably, particle is grafted on the skeleton of triol.Dispersion triols contains the organic polymer particle of capacity, makes described compositions table reveal the required character of discussing herein.Preferably, it is organic polymer particle multipolymer more than about 20 weight % that dispersion triols comprises based on dispersion, and preferred about 30 weight % are above and more than more preferably about 35 weight %.Preferably, it is organic polymer particle below about 60 weight % that dispersion comprises based on dispersion, and preferred about 50 weight % are following and below more preferably about 45 weight %.Polyvalent alcohol (two pure and mild triols, and dispersed polyol) is present in the composition with the amount of the most isocyanate groups reaction of isocyanic ester being enough to, thereby stays the isocyanate groups of enough A components corresponding to composition.

Have in the embodiment of the SOLID ORGANIC particle that is grafted on it at the isocyanate-reactive prepolymer, the amount of organic filler is enough to provide the required character of discussing herein to the composition of combination.Preferably, the isocyanate-functional prepolymer contains the above SOLID ORGANIC particle of 2 weight % of having an appointment, and more than more preferably about 5 weight %, and most preferably is more than about 10 weight %.Preferably, the isocyanate-functional prepolymer contains the following SOLID ORGANIC particle of the 26 weight % that have an appointment, and more preferably about 22 weight % are following and most preferably be below about 18 weight %.In first part is the prepolymer that is grafted to the organic filler on it that has that one or more isocyanate-functional prepolymers of existing in the A part can comprise 0 weight % to 100 weight %.Important feature is the gross weight of the organic filler that exists in the composition of the combination described in front.Therefore, can use isocyanate function polymkeric substance with the organic polymer particle that is grafted on it and the mixture with isocyanate-functional prepolymer of the organic filler that is grafted on it, condition is the organic filler that has aequum in total composition.

The isocyanate-functional prepolymer is present in the first part with q.s, thereby bond property is provided and has improved the required character of the present composition of describing herein for composition.Preferably, the isocyanate-functional prepolymer is present in the first part with the amount that accounts for more than the about 10 weight % of first part, more than more preferably about 20 weight %, and most preferably is more than about 30 weight %.Preferably, the isocyanate-functional prepolymer is present in the first part with the amount that accounts for below the about 90 weight % of first part, below more preferably about 70 weight %, and most preferably is below about 50 weight %.The mixture that uses the isocyanate-functional prepolymer and wherein the part of isocyanate-functional prepolymer have in the embodiment that is grafted to the organic filler on it, isocyanate-functional prepolymer with the organic filler that is grafted on it is present in the first part with the amount that accounts for more than the about 10 weight % of first part, more than more preferably about 20 weight %, and most preferably be more than about 30 weight %.Preferably, described isocyanate-functional prepolymer with below about 60 weight % and the amount that most preferably is below about 50 weight % be present in the first part.

For the purpose of the modulus of the composition that improves cured form, first part is that the A part can further comprise one or more polyfunctional isocyanates." multifunctional " of using in the context of isocyanic ester is meant that functionality is the isocyanic ester more than 2.2.The polyfunctional isocyanate can be that specified functionality is about monomer, oligomeric or polymeric isocyanic ester more than 2.2.More preferably, the polyfunctional isocyanate has about specified functionality more than 2.7.Preferably, the polyfunctional isocyanate has about below 4 and most preferably be about specified functionality below 3.2.The polyfunctional isocyanate can be have with composition in the isocyanate-reactive compound that uses reactive and improve any isocyanic ester of the modulus of curing composition.The polyfunctional isocyanate can make monomer; The tripolymer of monomeric diisocyanate, chlorinated isocyanurates or biuret; Oligopolymer or polymkeric substance, the some unitary reaction product of one or more monomeric diisocyanates.Preferred polyfunctional isocyanate's example comprises with trade mark and name DESMODUR

N3300 and N-100 are available from the tripolymer of the hexamethylene diisocyanate of Bayer, and polymeric isocyanate, such as polymeric MDI (methylenediphenyl diisocyanates), such as by Dow Chemical with trade mark PAPI ^TMThose that sell comprise PAPI ^TM20 polymeric isocyanate.The polyfunctional isocyanate exists with the amount of the modulus that is enough to influence curing composition of the present invention.If use too much, the solidification rate of composition unacceptably falls slowly.If use very little, then can not realize required modulus level.Based on composition is the weight of A-and B-aspect (side), the polyfunctional isocyanate preferably with more than about 0.5 weight %, more preferably more than about 1.0 weight % and the amount that most preferably is more than about 1.4 weight % exist.Based on composition is the weight of A-and B-aspect, the polyfunctional isocyanate preferably with below about 8 weight %, more preferably below about 5 weight % and the amount that most preferably is below about 2.0 weight % exist.

First part is that the A part can further comprise one or more at the about 23 ℃ of isocyanate-functional prepolymers that contain one or more polyester polyvalent alcohols for solid of envrionment temperature.The fusing point of polyester polyvalent alcohol makes prepolymer that enough green strengths are provided, thereby prevents substrate owing to gravity moves relative to each other, and makes that prepolymer is a solid in envrionment temperature.Window is being installed in aspect vehicle or the buildings, the polyester prepolymer prevents the slip of window after installing.Preferably, the fusing point of polyester polyol is about more than 40 ℃, and is also more preferably about more than 45 ℃ and most preferably be about more than 50 ℃.Preferably, the fusing point that polyester polyol shows is about below 85 ℃, most preferably is about below 60 ℃, and more preferably about below 70 ℃.The polyester isocyanate prepolymer can use one or more polyester polyol preparations.The amount of polyester polyol in prepolymer is to be enough to composition of the present invention is provided required green strength, is enough to the amount that makes it remain solid and the required rheological of composition is provided.Preferably, polyester polyol is being more than about 70 weight % based on prepolymer weight and the amount more than more preferably about 80 weight % is present in the polyester polyol kind isocyanate prepolymer.Preferably, polyester polyol is being below about 95 weight % based on prepolymer weight and the amount below more preferably about 90 weight % is present in the polyester polyol kind isocyanate prepolymer.Preferably, polyester polyol kind isocyanate prepolymer is to be present in the binder composition based on the amount more than the 2 weight % more than about 1 weight % of prepolymer weight and most preferably from about.Preferably, polyester polyol kind isocyanate prepolymer with below about 5 weight % and the amount that most preferably is below about 3 weight % be present in the binder composition.Polyester polyol can be any polyester polymers, and described polyester polymers satisfies the character requirement that limits, promptly in the envrionment temperature crystallization and in temperature required scope fusion.Preferred polyester type polyvalent alcohol is by straight chain diacid and straight diol preparation.Preferred diacid is a hexanodioic acid.Preferred glycol is C _2-6Glycol, wherein butyleneglycol, pentanediol and hexylene glycol are most preferred.The polyester polyisocyanate prepolymer can use previously described method and isocyanic ester preparation.Preferred polyester type polyvalent alcohol can be with trade(brand)name DYNACOLL and name 7360 and 7330 available from EVONIC Industries, and wherein more preferably 7360.

The second section of composition of the present invention comprises one or more compounds that contains isocyanate-reactive group.Preferably, isocyanate-reactive group is the group that contains active hydrogen.Isocyanate-reactive group reacts with the isocyanate functional group by contacting with the isocyanate functional group of first part, thereby composition is solidified.The compound that contains isocyanate-reactive group can be contain with the isocyanate-functional prepolymer on the compound of such isocyanate-reactive group of isocyanate reaction.The term of Shi Yonging " isocyanate-reactive compound " comprises any organic compound with at least two isocyanate-reactive parts in this article, such as the compound that contains the active hydrogen part, or the imino-functional compound.For the present invention, the part that contains active hydrogen is meant the part of hydrogen atoms, described hydrogen atom according to Wohler at Journal of the American Chemical Society, 49 volumes, the Zerewitinoff test of describing in 3181 pages (1927) is owing to its position in molecule shows tangible activity.The example of such active hydrogen part is-COOH ,-OH ,-NH ₂,-NH-,-CONH ₂,-SH and-CONH-.Preferably contain compound bearing active hydrogen and comprise polyvalent alcohol, polyamines, polythiol and polyprotonic acid.In another embodiment, containing compound bearing active hydrogen can be the active hydrogen functional prepolymer, and described active hydrogen functional prepolymer is that one or more polymeric polyisocyanates and one or more contain compound bearing active hydrogen in the reaction product under the condition as follows: excessive reactive with active hydrogen group is so that the reactive group on the gained prepolymer is to have reactive amount that contains compound bearing active hydrogen with isocyanate groups to exist.Suitable imino-functional compound is to have those of at least one imino-end group in each molecule,, describes in 279 at United States Patent (USP) 4,910 such as for example, and this United States Patent (USP) is attached to this with its full content by reference.Preferably, isocyanate-reactive compound is the end capped polyvalent alcohol of polyvalent alcohol or amine, more preferably polyether glycol or polyether polyamine.In a preferred embodiment, contain the polyvalent alcohol of isocyanate-reactive group or have the prepolymer of isocyanate-reactive group and one or more chain extension agents or linking agent and/or the end capped polyvalent alcohol of one or more amine are united use.The compound that contains isocyanate-reactive group is present in the second section of composition of the present invention with competent amount, thereby by making composition curing and give institute's composition required composition character with isocyanate functional compound's reaction in two portions when contact that makes composition.Preferably, one or more compounds that contain isocyanate-reactive group with more than the about 10 weight % that account for second section, more preferably more than about 20 weight % and the amount that most preferably is more than about 30 weight % be present in the second section.Preferably, one or more compounds that contain isocyanate-reactive group with below the about 100 weight % that account for second section, more preferably below about 60 weight % and the amount that most preferably is below about 50 weight % be present in the second section.Comprise in the embodiment of one or more compounds at second section with isocyanate-reactive group with the organic filler that is grafted on it, second section also comprises one or more compounds with isocyanate-reactive group that does not have the organic filler that is grafted on it, that is, such compound does not contain solid.In a preferred embodiment, do not contain amount that solid do not have the isocyanate-reactive compound that is grafted to the organic filler on it account for second section about 5 to about 30 weight %.

Except other contains the compound of isocyanate-reactive group, the second section of composition of the present invention is that the B part can also comprise the low-molecular weight compound that one or more have plural isocyanate-reactive group and hydrocarbon skeleton, and wherein said skeleton can further comprise one or more heteroatomss.Such low-molecular weight compound can be a compound as known in the art, and such as chain extension agent, such compound is two functional.Such low-molecular weight compound can be that also compound known is such as linking agent in the art, and such compound on average has the active hydrogen group/compound more than 2.Heteroatoms in skeleton can be oxygen, sulphur, nitrogen or their mixture, and wherein oxygen, nitrogen or their mixture are preferred, and oxygen is most preferred.Preferably, the molecular weight of low-molecular weight compound is about below 120 and more preferably about below 100.Preferably, low-molecular weight compound comprises one or more polyfunctional alcohols, multifunctional alkanolamine; One or more adductss of polyfunctional alcohol and oxirane; One or more adductss of multifunctional alkanolamine and oxirane; Or their mixture.Preferred low-molecular weight compound is to contain one or more heteroatomic straight chain hydrocarbon in skeleton.In preferred polyfunctional alcohol and multifunctional alkanolamine, ethylene glycol, propylene glycol, butyleneglycol, hexylene glycol, heptanediol, ethohexadiol, glycerine, TriMethylolPropane(TMP), tetramethylolmethane, neopentyl glycol, thanomin and Propanolamine are arranged.In the adducts that preferably contains oxirane, the pure and mild oxyethane of the hydroxyl that has more than 3 or the adducts of propylene oxide units are arranged.Preferred low-molecular weight compound comprises ethylene glycol, propylene glycol, butyleneglycol, hexylene glycol, ethohexadiol, glycerine, TriMethylolPropane(TMP), diethanolamine, trolamine, two-Yi Bingchunan, three-Yi Bingchunan, or the like.Can use the blend of various low-molecular weight compounds.Preferably, except other has the compound of isocyanate-reactive group, low-molecular weight compound with greater than 0 weight %, more preferably more than about 0.3 weight %, the amount that most preferably is more than about 0.5 weight % is present in the second section of the present composition.Preferably, low-molecular weight compound is with below about 10 weight %, and more preferably about 5 weight % are following and most preferably be the following amount of about 3 weight % and be present in the second section of composition of the present invention.

The second section of composition can further comprise one or more polyester polyols, such as previously described those.Polyester polyol can add with the amount of the green strength that is enough to improve contacted composition of the present invention.If exist, then polyester polyol preferably with more than about 1 weight % and the amount more than more preferably about 2 weight % exist.If exist, then polyester polyol preferably with below about 15 weight %, more preferably below about 8 weight % and the amount that most preferably is below about 3 weight % exist.

Second section is that the B part can also comprise the polyoxyalkylene polyamines, and described polyoxyalkylene polyamines has the amido/polyamines more than 2.Such compound can play a part jelling agent as described in this article.Preferably, the polyoxyalkylene polyamines has 2 to 4 amine/polyamines, most preferably is 2 to 3 amine/polyamines.Preferably, the weight-average molecular weight of polyoxyalkylene polyamines is about more than 200 and most preferably be about more than 400.Preferably, the weight-average molecular weight of polyoxyalkylene polyamines is about below 5,000 and most preferably be about below 3,000.In preferred polyoxyalkylene polyamines, it is about 400 JEFFAMINE that molecular weight is arranged ^TMT-403 poly(propylene oxide) triamine, and molecular weight is about 400 JEFFAMINE ^TMThe D-400 Polypropylene oxide diamine.The polyoxyalkylene polyamines is to be enough to preventing that the amount of the sagging (sagging) of composition when mixing and use from existing.Preferably, the polyoxyalkylene polyamines with more than about 0.2 weight %, more preferably more than about 0.3 weight % and the amount that most preferably is more than about 0.5 weight % be present in the composition of the present invention.Preferably, the polyoxyalkylene polyamines with below about 6 weight %, more preferably below about 4 weight % and the amount that most preferably is below about 2 weight % be present in the composition of the present invention.

Each part of composition preferably comprises one or more fillers.Filler adds for various reasons, and can use the filler of one or more types in the part of composition of the present invention.Can add filler such as clay, aluminum oxide, Wingdale, talcum, lime carbonate, carbon black, silica and pearlstone, be used for enhancing composition, be used to give suitable viscosity and rheological, and be used to reach the cost of various piece (parts) of composition and composition and the balance between the required character.One group of preferred filler of available is to give the cost of each part and the equilibrated filler between the viscosity among the present invention.In can be used for the filler of this purpose, talcum, lime carbonate and kaolin are arranged.The preferably uncoloured filler of such filler, and amount use to be enough to give the viscosity and the balance accepted between the cost of prescription and realize the required character of composition.Preferred uncoloured filler comprises lime carbonate or kaolin.The lime carbonate that can use in the present invention is the lime carbonate of standard.The lime carbonate of such standard is untreated, that is, they are that other chemical of no use is handled and modification such as organic acid or organic acid ester.Kaolin is also referred to as kaolinite and comprises by chemical formula Al ₂Si ₂O ₅(OH) ₄The compound of expression, and it is usually expressed as the clay size, flaky, sexangle crystal most.Preferably, but uncoloured filler exist with the amount that is enough to give composition and is suitable for taking out the rheological of tackiness agent as pump.Preferably, uncoloured filler most preferably is the above amount of about 15 weight parts and is present in the part 1 with more than about 8 weight parts.Preferably, uncoloured filler with below about 22 weight parts, the amount that most preferably is below about 18 weight parts is present in the part 1.

The part of the present composition can also comprise reinforcing filler, and described reinforcing filler exists for intensity and the rheological of improving composition.The preferred classes of reinforcing filler is a carbon black.Reinforcing filler exists with the amount that is enough to enhancing composition and improves the rheological of composition.In automobile was used, the non-conductive impedance that is understood to mean composition usually was at least 10 ¹⁰Ohm-cm.Preferably, reinforcing filler exists so that the part of described composition is non-conductive amount.If it is too many that some reinforcing filler exists such as carbon black, then composition may be an electroconductibility.When carbon black was used as reinforcing filler, employed carbon black can be a Standard carbon blacks.Standard carbon blacks is not for giving its carbon black of non-conductive surface-treated especially or oxidation.One or more non-conductive carbon blacks can be united use with Standard carbon blacks, but such comprising may increase unnecessary cost.The amount of Standard carbon blacks in composition provides the amount of required color, viscosity, sag resistance and intensity.If dielectric composition expects that then Standard carbon blacks can be that dielectric content uses with composition.Based on the weight of component, reinforcing filler preferably with based on each component at least about 5 weight %, more preferably be present in any component or two components at least about 10 weight % and the amount at least about 12 weight % of most preferably being.Based on the weight of component, reinforcing filler preferably be no more than about 30 weight %, more preferably be no more than about 25 weight % and most preferably be the amount that is no more than about 18 weight % be present in arbitrary or both components in.If the use graphitized carbon black must be noted that then the concentration that remains in the total composition is lower than about 18 weight %, is higher than 10 with the impedance that prevents composition ¹⁰Ohm-cm, the composition that is lower than this amount is considered to dielectric.Standard carbon blacks is known in this area, and comprise can be available from the RAVEN of Colombian ^TM790, RAVEN ^TM450, RAVEN ^TM500, RAVEN ^TM430, RAVEN ^TM420 and RAVEN ^TM410 carbon blacks and can be available from the CSX of Cabot ^TMCarbon black and can be available from the PRINTEX of Degussa ^TM30 carbon blacks.Non-conductive carbon black is known in the art, and comprise can be available from the RAVEN of Colombian ^TM1040 and RAVEN ^TM1060 carbon blacks.

Filler in another kind of one or two part that can be used for composition is the clay that adds for the cost benefit, viscosity and the dielectric purpose that improve composition of the present invention.Can be used for preferred viscosities among the present invention and comprise kaolin, surface-treated kaolin, incinerating kaolin, aluminosilicate and surface-treated anhydrous aluminosilicate.But clay can use with any form that promotes pump to take out the prescription of tackiness agent.Preferably, clay mixes with the powder of pulverizing, the bead of jet drying or the form of fine grinding particle.Clay can with more than the about 0 weight % that accounts for the present composition, more preferably more than about 10 weight % and the amount more than more preferably about 18 weight % use.Preferably, clay uses with the amount below the 40 weight % below the about 22 weight % that account for the present composition and more preferably from about.

Binder composition can also comprise the filler that plays a part thixotropic agent (rheologic additive).Such thixotropic agent is well known to those skilled in the art, and comprises pyrogenic silica or the like.Thixotropic agent can add in the arbitrary part or two portions of composition with the amount that is enough to produce required rheological property.Preferably, based on the weight of the present composition, thixotropic agent with more than about 0 weight % and the amount more than preferred about 1 weight part exist.Preferably, based on the weight of the present composition, optional thixotropic agent with below about 10 weight % and the amount below more preferably about 2 weight % exist.

One or two part of the present composition can also comprise the catalyst for reaction that is used for isocyanate moiety and water or contains compound bearing active hydrogen well known by persons skilled in the art.Preferably, catalyzer is not volatility under envrionment conditions.These compounds are known in the art.Preferably, to be arranged in the second section of composition be B part to catalyzer.Preferred catalyzer comprises organometallic compound, amines catalyst or their mixture.Preferably, use the mixture of organometallic compound and amines catalyst.In preferred organo-metallic catalyst, metallic bond alkanol hydrochlorate, metal acetate, metal acetylacetonates and tertiary amine are arranged.Preferred metallic bond alkanol phosphate catalyst comprises bismuth, zinc, potassium and sodium alkanol hydrochlorate, such as Bismuth Octoate, neodecanoic acid bismuth, zinc octoate, potassium octanoate and Sodium octoate.Metal acetate comprises potassium acetate.The metal acetyl acetylacetonate comprises acetylacetonate iron and diacetyl acetonization dibutyl tin.Preferred metal salt catalyst comprises bismuth or tin as metal, wherein tin most preferably.Preferred amine catalyst comprises dimorpholino dialkyl ether, two ((dialkyl group morpholino) alkyl) ether, two-(2-dimethylamino-ethyl) ether, triethylenediamine, five methyl diethylentriamine, N, N-dimethylcyclohexylamine, N, N-lupetazin 4-methoxy ethyl morpholine, N-methylmorpholine, N-ethylmorpholine, and their mixture.Preferred dimorpholinodialkyl ethers is a dimorpholino diethyl ether.Preferred two ((dialkyl group-morpholino) alkyl) ether is (two-(2-(3,5-thebaine generation) ethyl) ether).Tertiary amine uses with the amount of the reaction that contains compound bearing active hydrogen to be enough to the catalysis isocyanate groups, preferably, tertiary amine with the weight based on composition is more than about 0.15 weight part, most preferably from about more than 0.2 weight part and below about 2.0 weight parts, more preferably from about below 1.75 weight parts, also more preferably from about below 1.0 weight parts, most preferably from about the amount below 0.4 weight part is used.Organometallic compound class catalyzer in use, preferably with the weight based on binder composition be more than about 0 weight part, more preferably from about more than 0.1 weight part, also more preferably from about more than 0.2 weight part and most preferably from about the amount more than 0.4 weight part use.Such organometallic compound class catalyzer preferably with the weight based on binder composition be below about 5 weight parts, more preferably from about below 2.0 weight parts, also more preferably from about below 1 weight part and most preferably from about the amount below 0.6 weight part use.

A partly is that resin part and B partly are that arbitrary in the solidified nature part or both can comprise pigment, stablizer UV stabilizer, UV stabilizer, antioxidant and be present in other additive in curable polyurethane formation composition and the tackiness agent usually.For the premature hydrolysis of the wet quick group that prevents the isocyanate-reactive component, filler and pigment should be before mixing with it finish-drying.

Curable compositions of the present invention can also comprise softening agent, rheological property is modified as required denseness.Such material should be anhydrous, for isocyanate groups be inert and with the polymkeric substance that exists be compatible.Softening agent can be arranged in arbitrary part.Suitable manufacturing methods is to know in this area, and preferred plasticizer comprises the O-phthalic acid alkyl ester, such as diisononyl phthalate or Di Iso Decyl Phthalate, the ester of partially hydrogenated terpenes, trioctyl phosphate, toluol sulfonamide, alkylsulphonic acid, adipic acid ester, Viscotrol C, toluene and alkylnaphthalene.The amount of softening agent in each part of curable compositions provides the amount of required rheological property.Amount disclosed herein is included in the prepolymer preparation process that contains isocyanic ester and those amounts of adding in the blending process of curable compositions.Preferably, based on the weight of the present composition, softening agent with more than about 0 weight %, more preferably more than about 5 weight % and the amount that most preferably is more than about 10 weight % be used for composition of the present invention.Based on the weight of the present composition, softening agent preferably with below about 45 weight % and the amount below more preferably about 40 weight % use.

Composition of the present invention can also comprise stablizer, and described stablizer plays a part the protection binder composition and avoids the influence of moisture, suppresses progress thus and prevents crosslinked too early in the isocyanic ester in the curable formulations.The stablizer that is used for polyurethane curable two portions composition well known by persons skilled in the art can use in this article.In these stablizers, comprise diethyl malonate, alkylphenol alkylide, tosic acid isocyanic ester, Benzoyl chloride and alkyl orthoformate (orthoalkyl formates) or molecular sieve.Based on the weight of composition of the present invention, such stablizer preferably uses with the amount more than the 0.8 weight % more than about 0.1 weight %, more than preferred about 0.5 weight % and more preferably from about.Based on the weight of composition of the present invention, such stablizer is with below about 5.0 weight %, more preferably from about below the 2.0 weight % and most preferably from about the amount below the 1.4 weight % is used.

Composition of the present invention can also comprise adhesion promotor, such as the 0055th to 0065 section and the U.S.6 of Hsieh in the U.S. Patent Publication 2002/0100550 of Mahdi, 015,475 the 5th hurdles the 27th walk to those disclosed in the 6th hurdle the 41st row, and these United States Patent (USP)s and patent are announced and be combined in this by reference.The usage quantity of these adhesion promotors also is disclosed in these documents and is combined in this by reference.

Two portions preferably combination of composition of the present invention makes the equivalent of isocyanate groups greater than the equivalent of isocyanate-reactive group.Preferably, select the amount of the isocyanate groups that provides by isocyanate-functional prepolymer and polyfunctional isocyanate, to be created in the required ratio of isocyanate groups and isocyanate-reactive group in the B part in the A part.Preferably, the ratio of isocyanate groups in component A and isocyanate-reactive group (such as, active hydrogen group) is at least about 1.1, more preferably from about more than 1.15, most preferably from about more than 1.2, and be not more than about 1.8, more preferably from about below 1.5, most preferably from about below 1.3.The functionality of two kinds of components is so that the gained cross-linking density of cure adhesive provides the mode of required modulus to regulate.

Part of the present invention or curable compositions can be prepared the component blend by using mode well known in the art together.Normally, component is carried out blend in suitable mixing tank.Such blend preferably under vacuum or inert atmosphere such as nitrogen or argon gas in, do not exist oxygen and atmospheric moisture to carry out under with the situation that prevents premature reaction.Such mixture maybe advantageously, adds softening agent, so that can easily mix and handle to the reaction mixture that is used for preparing the component that contains isocyanic ester.Alternatively, softening agent can add in the blend process of all components.Preferably, component is at about 20 ℃ to about 100 ℃, and more preferably about 25 ℃ are carried out blend to about 70 ℃ temperature.The composition blend is enough to prepare the time of the mixture of well blend, and preferred blend about 10 was to about 60 minutes.In case prepare described part or curable compositions, just they are packaged in the suitable containers, avoid the influence of atmospheric moisture and oxygen to protect them.Can cause the crosslinked too early of isocyanate-functional prepolymer with contacting of atmospheric moisture and oxygen.

Polymerisable compound of the present invention is used as two-part adhesive.The component of polymerisable compound is by blend, and this all will do when using these materials to carry out work usually like this.For two portions polymerisable compound that can be used as tackiness agent, such as the easiest those that use in the commercial and industrial environment of the present invention, the volume ratio when two portions are combined is preferably integer easily.Help the application of curable compositions when use comprises that static and dynamic blended routine is purchased decollator like this.Use this decollator of static mixing to be shown in United States Patent (USP) 4,538,920 and 5,082, in 147 (being combined in this by reference), and can be with trade(brand)name MIXPAC available from Conprotec, Inc. (Salem of New Jersey) or available from the Sulzer Quadro of the Sulzer Ltd of Switzerland.Typically, these decollators use a pair of tubular type receptor that is arranged side by side, and wherein each manages the part in two portions of all planning the reception polymerisable compound.Two stoppers, one of pipe, advance simultaneously (for example, manually or by hand braking ratcheting mechanism), be used for the content of pipe is discharged to the hollow elongated mixing section of common, this mixing section can also comprise the static mixer that is used to promote two portions blend.The polymerisable compound of blend is expressed in the substrate from mixing section.When using electrically driven (operated) equipment, can use dynamic mixing.In case pipe is drained, they can be replaced with new pipe, and coated technique continues.Volume ratio when two portions of polymerisable compound are combined is by official's diameter control.(size that customizes each stopper is with the inside of the pipe that is accommodated in fixed diameter, and stopper is advanced in the pipe with identical speed.) single decollator is planned to use with various two portions polymerisable compound usually, and the size of customization stopper, thereby send two portions of polymerizable compositions with favourable ratio of mixture.Some common ratio of mixture are 1: 1,2: 1,4: 1 and 10: 1.Preferably, two portions are with about 1: 1 ratio of mixture blend.

Preferably, blended two portions composition of the present invention has suitable viscosity, thereby allows to apply under the situation that does not have drippage.Preferably, the viscosity of two independent components should have the identical order of magnitude.Preferably, for using static mixing to carry out the blended composition, the viscosity of each component before mixing is about 10Pa.S (10,000 centipoise) more than, more than more preferably about 20Pa.S (20,000 centipoise), and most preferably be more than about 40Pa.S (40,000 centipoise).Preferably, the viscosity of blended two portions composition before solidifying is below about 150Pa.S (150,000 centipoise), below more preferably about 120Pa.S (120,000 centipoise), and most preferably is below about 100Pa.S (100,000 centipoise)." viscosity " used in this section was with 20 seconds of measuring at the cone-plate formula rheometer that uses 20mm diameter and 4 ° of angles ^-1Shearing rate determine.Higher viscosity needs dynamically to mix.For lower viscosity, the jelling agent that described component may need to be known in the art prevents the sagging of incured adhesives system.

As previously described, polymerisable compound of the present invention is used to various substrates are bonded together.Described composition can be used for porous and non-porous substrate are bonded together.Polymerisable compound after two portions contact is coated in first substrate, contacts with second substrate at the first suprabasil polymerisable compound afterwards.In preferred embodiments, with the cleaning surfaces of the coating present composition and chose wantonly before coating and activate and/or prime.Normally, composition of the present invention applies in the temperature that polymerisable compound can be pumped.Preferably, polymerisable compound of the present invention be used to apply about more than 0 ℃ temperature, more preferably about temperature more than 18 ℃ applies.Preferably, polymerisable compound of the present invention be used to apply about below 45 ℃ temperature, more preferably from about the temperature below 35 ℃ applies.Polymerisable compound begins to solidify by making two portions contact.Curing can promote by by means of convection heat, microwave heating or the like cure adhesive being applied heat.

Contacted composition preferably is used to bond glass to other substrate such as on metal or the plastics.In a preferred embodiment, first substrate is a glass window, and second substrate is a window frame.In another preferred embodiment, first substrate is a glass window, and second substrate is the windows of vehicles framework, and described vehicle preferably is used for the vehicle of mass transportation.Preferably, glass window is clean, and can have glass wiped joint band (glass wipe) or the priming paint that is coated on the zone for the treatment of adhesive binder.Window flange can be used the base coat priming.The composition of contact is applied to bead on the periphery of window, and described window is arranged that it will contact window flange when making in being placed on vehicle.The window that will have position contact composition thereon then is placed in the flange, and wherein Jie Chu composition is disposed between window and the flange.The composition bead of contact is the successive bead, and it plays a part the joint between sealing window and the window flange.The continuous bead of tackiness agent is so a kind of bead: the position of this bead makes bead terminal connect the continuous sealing that forms with in contact the time between window and the flange at each.Afterwards, the composition of contact is solidified.Composition of the present invention with have enough green strengths after substrate contacts, with prevent window after its assembling, be shorter than 90 minutes, more preferably be shorter than 60 minutes mobile.Composition of the present invention is particularly useful for and will be bonded in the substrate at the bottom of the big quality-base that is no more than about 120Kg greater than 20Kg.Using at the bottom of the big quality-base of a class of composition of the present invention is big window, such as those windows that use in the mass transportation vehicle.

In a preferred embodiment, composition of the present invention can be used for changing in structure or vehicle and the window in vehicle most preferably.First step is to remove previous window.This can be by the bead of cutting with the tackiness agent of old window fix in position, moves old window then and realize.Afterwards, with new window cleaning and priming.Can remove the old tackiness agent that is located on the window flange, but this is not necessarily essential, and in most of the cases, it is stayed on this position.Window flange is preferably used the base coat priming.Tackiness agent is coated to the periphery of window with bead form, and it will contact window flange when the position of described window makes in being placed on vehicle.To have tackiness agent position window thereon then and be placed in the flange, wherein tackiness agent is between window and flange.Adhesive bead is the successive bead, and it plays a part the joint between sealing window and the window flange and is used to make body structure to strengthen up to about 40%.The continuous bead of tackiness agent is such bead: its position makes bead in each terminal connection to be formed on the continuous sealing between window and the flange when contacting.Afterwards, tackiness agent is solidified.Tackiness agent shows strength development fast, and this (drive away) time that helps driving away fast, the described time is preferably 1 hour at about 0 ℉ (18 ℃) to the temperature applying adhesive of about 115 ℉ (46 ℃), and more preferably 30 minutes.Particularly, the windshield glass of installing under such condition satisfies the United States Federal's MotorVehicleSafetyStandard (United States Federal Motor Vehicles Safety Standard) (FMVSS) 212.

In one embodiment, composition of the present invention is preferred for the metal of metal, coating (using electrophoretic paint (e-coat) or paint systems), plastics, fibre reinforced plastics, timber and/or glassy bond together.In another embodiment, composition of the present invention can be used for the built-up type assembly is bonded on the car body or be bonded to one another.The example of built-up type assembly comprises vehicle assembly, such as door, window, roof assembly or vehicle body.Polymerisable compound of the present invention can also be used to exterior trimming parts or inside gadget is bonded on the vehicle body.

In some applications, polymerisable compound of the present invention can use with priming paint or activation wiped joint band (activation wipe).Priming paint or activation wiped joint band typically are applied on the surface of one or more substrates.Any solvent is allowed to vapor away, and polymerisable compound contacts with substrate then.Preferably, from priming paint or activation wiped joint band to be coated to polymerisable compound to time period of suprabasil coating be about more than 0.5 minute, more preferably about more than 1 minute, and most preferably be about more than 2 minutes.

Polymerisable compound can be bonded in some substrate under the situation of the surface that does not have priming paint or substrate without any other processing, the surface cleaning except.Polymerisable compound typically comprises sheet stock molded composites (SMC), fibre reinforced plastics in the substrate that does not need to be bonded under priming paint or the surface-treated situation on it, such as polyester, and the metal that coats, such as the aluminium and the steel of electrophoresis coating, and the tinsel of japanning.

Polymerisable compound of the present invention preferably shows enough green strengths, with after about 90 minutes, more preferably after about 60 minutes, most preferably after about 30 minutes, under the situation that applies power in not to substrate, substrate is kept together and relative to each other do not move.Polymerisable compound of the present invention preferably shows completely solidified after about 1 day of room temperature.Solidifying faster can be by realizing in the heating that is no more than about 120 ℃ temperature.Be lower than under 23 ℃ the situation, it is longer to become set time.The tensile strength after completely solidified that polymerisable compound of the present invention preferably shows, more than more preferably about 5MPa and most preferably is more than about 6MPa for more than about 4MPa.The lap shear strength after 2 hours that polymerisable compound of the present invention preferably shows, more than more preferably about 2MPa and most preferably is more than about 3MPa for more than about 1MPa, and wherein said lap shear strength is measured according to DIN 53283.The elongation at break after completely solidified that polymerisable compound of the present invention preferably shows is about more than 100%, and is more preferably about more than 200%, and most preferably is about more than 300%.The elongation at break after completely solidified that polymerisable compound of the present invention preferably shows is about below 350%.Elongation at break is measured according to DIN53504.

" molecular weight " of Miao Shuing is number-average molecular weight in this article, and it can be determined by gel permeation chromatography (being also referred to as SEC).For polyurethane prepolymer, it can also be as is known to persons skilled in the art recently calculates proximate data molecular weight by isocyanate compound and with the equivalent of the polyol compound of their reactions.Unless otherwise noted, all part and per-cent are that all be by weight and weight that be based on composition of the present invention.

Exemplary of the present invention

Provide the following examples to be used to illustrate the present invention, but these embodiment should not be considered to limit the scope of the invention.All parts and per-cent all are by weight, unless otherwise noted.The composition that uses in Zhi Bei the prepolymer is described in the table 1 in the following embodiments.

Table 1-composition

The polyether(poly)urethane prepolymer is by being prepared as follows: the molecular-weight average that mixes 22.571g is that the polyoxypropyleneglycol of 2000g/mol and the molecular-weight average of 33.132g are the polyoxytrimethylene triol of 4650g/mol.Add the softening agent of 33.779g.In addition, add the ditan 4 of 9.501g, 4 '-vulcabond.Afterwards, be added on the ortho-phosphoric acid of the 0.001g in the methyl ethyl ketone (MEK) of 0.009g and add the diethyl malonate of 1g.Then, whole mixture is heated to 50 ℃ in reactor, and adds the stannous octoate of 0.007g.To be reflected at 50 ℃ carried out 1 hour.Resulting polymers is known as NCO-prepolymer-1 in this article.

The polyether(poly)urethane prepolymer that contains the SAN-copolymer solids is by being prepared as follows: the SAN-that 60.58g is had a SAN-solids content of 40% altogether-polyoxytrimethylene triol, 31.98g softening agent, the 0.001g ortho-phosphoric acid in the methyl ethyl ketone of 0.009g be placed in the reactor.SAN is a styrene-acrylonitrile.By after the mixing, add the ditan 4 of 7.41g, 4 '-vulcabond.Once more will mixing.Then, reactor is heated to 50 ℃.Afterwards, add the 0.02g stannous octoate, and will be reflected at 50 ℃ and carry out 1 hour.Resulting polymers is known as NCO-prepolymer-2 in this article.

The polyether(poly)urethane prepolymer is by being prepared as follows: the molecular-weight average that mixes 38.699g is that the polyoxypropyleneglycol of 2000g/mol and the molecular-weight average of 18.516g are the polyoxytrimethylene triol of 4650g/mol.Add the softening agent of 31.854g.In addition, add the ditan 4 of 10.701g, 4 '-vulcabond.Afterwards, be added on the ortho-phosphoric acid of the 0.001g among the 0.009g MEK and the diethyl malonate of interpolation 0.213g.Then, whole mixture is heated to 50 ℃ in reactor, and adds the stannous octoate of 0.007g.To be reflected at 50 ℃ carried out 1 hour.The gained prepolymer is known as NCO-prepolymer-3 in this article.

This embodiment prepares U.S.5, the isocyanate-functional prepolymer of 852,103 embodiment 1.The polyether(poly)urethane prepolymer of reduced branching degree is by being prepared as follows: the molecular weight that mixes 363.68g is 2000 polyoxyalkylated glycol (polyoxylate diol) and the molecular weight that is dispersed in of 527.04g is a polyureas in 4500 the polyoxyalkylated triol.Be blended in the reactor by heated mixt to 55 and ℃ carry out.In mixture, add the ditan-4 of 160.6g, the stannous octoate of 4 '-vulcabond and 0.17g.Make whole mixture reaction 1 hour then.At last, in mixture, add the plasticizer phthalic acid diallyl ester of 525.44g, and continue to mix 1 hour.The gained prepolymer is known as NCO-prepolymer-4 in this article.

The composition of table 2 isocyanate-functional prepolymer

The preparation of the end capped prepolymer of OH-

The NCO-prepolymer-3 of 61.4g is placed in the reactor.In reactor vessel, add the 2 mercapto ethanol that is used for end capped 2.53g.Afterwards, be added on the 0.01g in the 0.139g toluene, and mixture is heated to 50 ℃ when stirring (steering).To be reflected at 50 ℃ carried out 1 hour.The prepolymer of gained is known as OH-prepolymer-1 in this article.In addition, the gained prepolymer is the thick substances that does not contain the free isocyanate functionality.

This example is U.S.5, the preparation of the OH-prepolymer composite of 852,103 embodiment 1.Hydroxyl-functional polyureas dispersive polyether(poly)urethane prepolymer is by following synthetic: make polyoxyalkylated two pure and mild polyureas dispersive polyoxyalkylated triol reactions.This mixture is stirred and be heated to 55 ℃, and add ditan-4,4 '-vulcabond and stannous octoate, and mixed other 30 minutes.Add plasticising reagent, i.e. softening agent (DAP), and mixture stirred other 30 minutes.The gained prepolymer is the thick substances that does not contain the free isocyanate functionality.Be used for preparing component editor's table below of every kind of hydroxyl-functional prepolymer.

The preparation of the A part of binder composition:

Four kinds of compositions that are used as the A part are by being prepared as follows: use isocyanate-functional prepolymer 1 to 4.Prepolymer (component 1) is placed in the planetary-type mixer, and outgased 30 minutes.Under the situation of composition A-2 and A-3, before the degassing, add component 2.Then, add the component 3 to 6 of appropriate amount.Afterwards, mixture was mixed 30 minutes under vacuum.At last, added component 7 to 10 and remix 15 minutes.

Table 3: binder composition A-component:

^*Relatively

The preparation of the B part of binder composition:

The partly solidified property of B composition uses the hydroxyl-functional prepolymer by being prepared as follows: component 1,5,6,7 and 8 is placed in the epicyclic mixer.Liquid ingredient was mixed 30 minutes in a vacuum.Then, add component 2,3 and 4 and under vacuum, mixed 30 minutes again.Afterwards, add component 9 or 10 and mixed 15 minutes.Every kind of compound all is presented in the table.

Table 4: binder composition B-component:

Characterizing method:

A and B partly are sampled in the barrel (cartridge) of 300ml, and are assembled in the outfit (kit) with dynamic mixing head, with assembling high-speed mixing electron beam gun (BETAGUN ^TM).With material being that 1: 1 ratio of mixture is extruded at a high speed based on volume.After 2 hours specific set time, according to described in standard ASTM D-3168, measuring lap shear strength.Paving (decking) performance measurement is as follows: 1cm height, 7mm is wide and 10cm is high trilateral bead are placed on the unprimed glass bar, and are placed on " the penetrometer PNR 6 " of SUR Berlin.Afterwards, the seamless unoccupied place of 5g counterweight with penetrometer is placed on the bead.Then, counterweight is discharged 5 seconds and allow to move in the material.Report mobile distance and this distance is called paving property (decking).After the bead placement is spread 15 minutes and 30 minutes out, determine paving property.Working hour measures as follows: the trilateral bead of 1cm height, the wide 7mm in bottom is expressed on the surface of stability 23 ℃ and 50% relative humidity).After extruding, monitoring period and be expressed to wooden scraper in the bead and be pulled away from.Determine the working hour by the time point that tackiness agent does not adhere on the scraper.

Table 5: working hour and lap shear strength

^*Relatively

Table 5 is described the various working hours of different tackiness agents.Composition of the present invention has confirmed long working hour and high lap shear strength (lap shear) in sample " adhesive A 1-B1 " and " adhesive A 3-B3 ".Comparative sample " adhesive A 2-B2 " and " adhesive A 4-B4 " by the known technology preparation also have long working hour and low lap shear strength, as " adhesive A 2-B2 ", or under the situation of " adhesive A 4-B4 ", high lap shear strength, but have the short working hour.

Table 6: paving property

	?A1-B1	A2-B2 ^*	A3-B3
				Paving property after 15 minute working hour	?mm	mm	mm
5℃	?2.2	4.0	2.4
				23℃	?2.2	3.2	2.1
40℃	?1.8	1.7	1.5
				Paving property after 30 minute working hour
5℃	?1.1	3.2	3.7
				23℃	?1.5	3.1	1.9
40℃	?0.9	0.2	1.0

Table 6 has shown the paving performance of several adhesive type." adhesive A 1-B1 " and " adhesive A 3-B3 " represented composition of the present invention, and " adhesive A 2-B2 " represented standard technique, and it is used to and need handles the application that farm labourer that intensity combines does the time with height.The all temps 15 that may occur in typical indoor and outdoor assembly installation process and after 30 minutes is determined the paving performance.Placed at bead and to have spread (15 minute working hour) out afterwards, the paving performance of sample " adhesive A 1-B1 " and " adhesive A 3-B3 " shows that paving property has reduction slightly in 5 to 40 ℃ temperature range." adhesive A 2-B2 " as standard technique produced 4 to 1.7mm big variation in this temperature range.Paving property demonstration after 30 minutes working hour: 1.1 to 0.6mm the minimum change of sample " adhesive A 1-B1 " in this temperature range." adhesive A 3-B3 " 5 ℃ of intrusions that higher 3.7mm is provided, but remain softer under the situation in 40 ℃ and 1mm paving.Conventional sample " adhesive A 2-B2 " provides 3.2 height to invade and has been inflexible at 40 ℃ at 5 ℃, thereby the intrusion of 0.2mm is provided.When invading greater than 0.9mm, the paving performance of tackiness agent is suitable.Generally speaking, tackiness agent of the present invention provides such effect: owing to good lap shear performance provides enough anti-glass slides, and provide enough anti-glass to sink to character on the flange.A part and B partly are inserted into the high-velocity electrons with suitable dynamic mixing head to be mixed in the coating rifle.Use this rifle, with the material in two pipes being that 1: 1 ratio is extruded at a high speed based on volume.Compare with standard prod, the paving property of described novel material is more stable in big temperature range.Dress paving property use penetrometer is measured, and the counterweight that its measurement limited in 5 seconds time limit is to the infiltration of material.

Claims

1. two portions composition, described composition comprises:

A) one or more isocyanate-functional prepolymers of (i) in a part; With

B) in second section (ii) one or more have the compound of isocyanate-reactive group;

(iii) one or more fillers select described filler to make that described composition is non-conductive; With

(iv) one or more catalyzer, described catalyzer is used for the reaction of isocyanate groups and isocyanate-reactive compound;

Wherein said one or more isocyanate-functional prepolymers and described one or more have arbitrary in the compound of isocyanate-reactive group or both have the SOLID ORGANIC particle that is grafted on it, make described composition contain to account for about 6 to about 13 weight % described SOLID ORGANIC particle of total composition.

2. two portions composition according to claim 1, wherein said second section comprise about 35 compounds to about 65 weight %, and described compound has the SOLID ORGANIC particle on the skeleton that is grafted to this compound.

3. two portions composition according to claim 1, wherein one or more isocyanate-functional prepolymers comprise about 0 SOLID ORGANIC particle to the skeleton that is grafted to described prepolymer of about 26 weight %.

4. according to each described two portions composition in the claim 1 to 3, wherein said solids comprise the thermoplastic polymer of thermoplastic polymer or modified rubber.

5. according to each described two portions composition in the claim 1 to 4, wherein said solids comprise the thermoplastic polymer of modified rubber.

6. according to each described two portions composition in the claim 1 to 5, wherein said solids comprise the multipolymer of monovinylidene aromatic monomer and conjugated diolefine, acrylate, methacrylic ester, unsaturated nitrile or their mixture.

7. according to each described two portions composition in the claim 1 to 5, wherein said solids comprise the multipolymer of unsaturated nitrile, conjugated diolefine and monovinylidene aromatic monomer, or the multipolymer of unsaturated nitrile and monovinylidene aromatic monomer.

8. according to each described two portions composition in the claim 1 to 7, wherein said second section also comprise about 5 to about 30 weight % one or more have the compound of isocyanate-reactive group, the described compound that one or more have isocyanate-reactive group does not contain solid.

9. according to each described two portions composition in the claim 1 to 8, wherein said one or more fillers comprise non-conductive carbon black, or make that described composition is the conductive carbon black of nonconducting amount.

10. according to each described two portions composition in the claim 1 to 9, wherein said one or more conductive carbon blacks exist with the amount below about 18 weight %.

11. according to each described two portions composition in the claim 1 to 10, wherein said one or more fillers comprise uncoloured filler, are suitable for being used as the rheological that pump is taken out tackiness agent but the amount of described uncoloured filler is enough to give described composition.

12. according to each described two portions composition in the claim 1 to 11, wherein said catalyzer comprises one or more organometallic compounds or amine.

13. two portions composition according to claim 13, wherein said catalyzer comprise one or more organometallic compounds and one or more amine.

14. according to claim 12 or 13 described two portions compositions, wherein said organometallic compound comprises one or more tin compounds.

15. according to each described two portions composition in the claim 1 to 14, wherein said B part also comprises the polyester polyvalent alcohol.

16. according to each described two portions composition in the claim 1 to 15, wherein said A partly is included in the isocyanate-functional prepolymer of the residue that has polyester polyol on the skeleton.

17. according to each described two portions composition in the claim 1 to 16, wherein said B part also comprises chain extension agent or linking agent.

18. according to each described two portions composition in the claim 1 to 17, wherein said A part also comprises the polyfunctional poly isocyanic ester.

19. according to each described two portions composition in the claim 1 to 18, wherein the ratio of described isocyanate groups in the A part and the described isocyanate-reactive group in the B part was greater than 1.1: 1.0.

20. one kind is used for method that plural substrate is bonded together, described method comprises: make two portions contact according to each described composition in the claim 1 to 19, contact with plural substrate with the contacted part with composition, the contacted part of wherein said composition is arranged between the substrate so that described substrate is bonded together.

21. method according to claim 20, one of them substrate is a glass, and another substrate comprises the structure with glassy bond.

22. method according to claim 21, wherein said structure are buildingss or are used for conveying objects and/or people's equipment.

23. method according to claim 22, wherein agglutinating glass is window.

24. method according to claim 23, wherein said window has greater than about 20 to about 120 kilograms quality.

25. according to each described two portions composition in the claim 1 to 19, described two portions composition is in case contact will show about 8 to about 30 minutes open hour.

26. according to each described two portions composition in the claim 1 to 19,2 hour meters of described two portions composition after contact reveal the lap shear strength more than about 2.0MPa.